CN101260272A - Water-based single-component paint and multilayer film forming method - Google Patents

Water-based single-component paint and multilayer film forming method Download PDF

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Publication number
CN101260272A
CN101260272A CNA2008100834934A CN200810083493A CN101260272A CN 101260272 A CN101260272 A CN 101260272A CN A2008100834934 A CNA2008100834934 A CN A2008100834934A CN 200810083493 A CN200810083493 A CN 200810083493A CN 101260272 A CN101260272 A CN 101260272A
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water
based single
compound
methyl
acrylic resin
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野口隆
安达尚人
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • B05D7/532—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The invention provides water-based one package coat comprising acrylic resin having specific long chain primary hydroxyl-containing side chains as crosslinking functional groups and a solubility parameter of 9.30-11.20, and blocked polyisocyanate compound having a solubility parameter of 9.00-11.50, the difference DeltaSP between the solubility parameter (SP1) of the acrylic resin and the solubility parameter (SP2) of the blocked polyisocyanate compound (DeltaSP=(SP1)-(SP2)) being within a range of from -0.80 to 1.50.

Description

Water-based single-component paint and multilayer film forming method
Technical field
The present invention relates to water-based single-component paint all excellent aspect curability, film performance, coatingsurface slickness and water-dispersion stability and the method that forms multilayer film with this water-based single-component paint.
Background technology
Recently, the environmental problem in the global range attracts great attention.In automotive industry, also take the lead in studying the countermeasure of environmental problem in the manufacturing step.The automobile making step is brought Global warming, produces the problem of industrial waste and discharging volatile organic compounds (VOC) and so on.Particularly, most of VOC discharge in application step, therefore press for to reduce VOC.
Car body covering part generally all scribbles multilayer film, is filmed and cover is filmed and constituted by cataphoresis primer film, centre, and purpose is to give solidity to corrosion and attractive in appearance.From reducing the viewpoint of VOC discharging, encourage to use water-based paints as centre and overlay coating.For example, from the viewpoint of film performance and coatingsurface slickness, as will considering to contain the transparent decorations coating compositions of water two-component that polyisocyanate compound is a linking agent as the transparent decorations lacquer of overlay coating.For example, disclosing there to be the polyisocyanate compound that is emulsified in the special polyol component is that the two-pack decorations coating compositions of feature (sees that for example, JP Hei 8 (1996)-32851B).But said composition owing to be two-component coating, need be mixed the polyisocyanate compound as linking agent at the eve of use decorations lacquer, and is subjected to the restriction of Apparatus and operation method.Also have a problem to be, decorations coating compositions is formed films from this, for example, prevents that atmospheric aging aspect performance is good inadequately.
On the other hand, blocked polyisocyanates compound commonly used is a linking agent in containing the onepot coating of polyisocyanate compound, and because the blocked polyisocyanates compound generally is hydrophobic, and it is not enough that it tends in water base decorations lacquer dispersion stabilization.Owing to be difficult to homodisperse blocked polyisocyanates compound in decorations lacquers, so for example, JP 2004-515571A proposes, it is dispersible to utilize the polyvalent alcohol of specific amido-containing acid ester base to make it to become water.And, need a large amount of urethane resins in order to obtain stable dispersion stabilization, and therefore can't obtain satisfied curability, cause the physicals deficiency of filming thus.
JP 11 (1999)-512772A also disclose the water dispersible end capping polyisocyanate compound that utilizes specific end-capping reagent to make.But owing in blocked polyisocyanates, introducing hydroxyl by realizing with the isocyanic ester radical reaction, thus the isocyanate group concentration in gained blocked polyisocyanates compound reduced, its result, curability has reduced.And still have another problem: because the high polarity of compound, the consistency of compound and base resin has reduced, thereby has damaged outward appearance.
The water-based single-component paint that contains the blocked polyisocyanates compound and be linking agent causes curing reaction after removing end-capping reagent.Remove when incomplete, another problem of bringing is, can not obtain enough curability, causes unsatisfied film performance thus.And, remove easily and the evaporable top layer of filming at end-capping reagent, reaction is carried out than faster in the layer, this has just reduced the concentration of film coated surface cohesiveness-participation functional group, and, when another layer decorations lacquer of coating on cured coating film surface, agglomerability surperficial and last coating film the deficiency that can become.
Summary of the invention
An object of the present invention is to provide in curability; Film performance is as hardness, acid resistance and scratch resistance etc.; The all excellent water-based single-component paint of film coated surface slickness and water-dispersion stability aspect; And the method that forms multilayer film with this water-based single-component paint.
We are to the base resin in the water-based single-component paint with as hydrophobic blocked polyisocyanates compound and its performance of linking agent, done further investigation as the dependency between curability, agglomerability, coatingsurface slickness and the water-dispersion stability etc., have now found that, above-mentioned purpose can realize with the water-based single-component paint that comprises following component: as the acrylic resin of base resin, it contains the side chain of long-chain hydroxyl, as C at least 4Uncle's hydroxyalkyl, C at least 4Primary hydroxyl polyoxyalkylene or analogue are crosslinking functionality, with and solubility parameters drop in the specified range; As the blocked polyisocyanates compound of linking agent, its solubility parameters drops in the specified range; And wherein the difference of the solubility parameters of the solubility parameters of acrylic resin and blocked polyisocyanates compound drops in the specified range.Finished the present invention thus.
Therefore, the invention provides water-based single-component paint, it is characterized in that, it is the decorations coating compositions that comprises following component:
(1) acrylic resin (A) by the following component gained of copolymerization
(a) (methyl) acrylate of at least a hydroxyl by following formula (I) expression of 20～60 quality %:
Figure A20081008349300061
Wherein,
R 1Represent hydrogen or methyl and
R 2Represent C at least 4Uncle's hydroxyalkyl, C at least 4The organic substituent of primary hydroxyl polyoxyalkylene or following formula (II) expression
Figure A20081008349300062
Wherein, R 3Represent hydrogen or methyl, 1 is 2～5 integer, and k is 1～7 integer;
(b) at least a vinyl monomer that contains carboxyl, sulfonic group or phosphate of 0.7～15 quality %; With
(c) but at least a other copolyethylene monomer of 25～79.3 quality %;
Described tree refers to that the hydroxyl value of (A) is that 110～200mgKOH/g and acid number are 5～50mgKOH/g;
With
(2) at least a blocked polyisocyanates compound (B),
The solubility parameters (SP1) that also is acrylic resin (A) is 9.30～11.20, the solubility parameters (SP2) of blocked polyisocyanates compound (B) is 9.00～11.50, and the difference Δ SP (Δ SP=(SP1)-(SP2)) of the solubility parameters (SP2) of the solubility parameters (SP1) of acrylic resin (A) and blocked polyisocyanates compound (B) is in-0.8～1.50 scopes.
Blocked polyisocyanates compound (B) comprise the end capped polyisocyanate compound of azole compounds and
This decorations coating compositions also includes machine tin compound and/or bismuth compound as catalyzer.
The present invention also provides to be included in and wants to be coated with on the coated object one deck priming paint and the multilayer film forming method of layer of transparent decorations lacquer at least at least, it is characterized in that being coated with above-mentioned water-based single-component paint as surface transparent decorations lacquer.
The present invention also provides the multilayer film that comprises following steps forming method: coated heat solidity water base paint compositions is a priming paint on the coated object wanting, the above-mentioned water-based single-component paint of coating is transparent decorations lacquer, while cured base enamelled coating and Clear coating then on uncured coatingsurface.
According to the present invention, in water-based single-component paint, play the solubility parameters (SP1) of the acrylic resin of base resin effect and as the solubility parameters (SP2) of the blocked polyisocyanates of linking agent all in specified range, poor (Δ SP=(SP1)-(SP2)) of these solubility parameters is little of-0.8～1.50, so base resin and linking agent are highly compatibles.Compare with the water-based single-component paint that to contain traditional blocked polyisocyanates compound be linking agent, in product of the present invention, the blocked polyisocyanates compound can stably be dispersed in the water base decorations lacquer, and therefore this product has good water-dispersion stability and film coated surface slickness.
In addition, because the acrylic resin that plays the base resin effect contains the side chain that specified quantitative contains the long-chain hydroxyl, as C at least 4Uncle's hydroxyalkyl, C at least 4Primary hydroxyl polyoxyalkylene or analogue, water-based single-component paint of the present invention has enough curability.Also because as the solubility parameters of the blocked polyisocyanates of linking agent in specified range, so can obtain filming of excellent propertys such as hardness and acid resistance.And the reactivity that participates in the residual hydroxy groups of agglomerability on film coated surface has increased, and its effect is, when another layer decorations lacquer of cured coating film surface coated, it and on the agglomerability (resurfacing agglomerability) of filming be improved.
Detailed Description Of The Invention
Explain water-based single-component paint of the present invention (after this can be referred to as " these decorations coating compositions ") and multilayer film forming method in more detail below.
Water-based single-component paint
Water-based single-component paint of the present invention is characterised in that and comprises at least a acrylic resin as base resin (A) and as the blocked polyisocyanates compound (B) of linking agent, described acrylic resin (A) contains the side chain of long-chain hydroxyl, as C at least 4Uncle's hydroxyalkyl, C at least 4Primary hydroxyl polyoxyalkylene or analogue, as crosslinking functionality, with and solubility parameters in specified range; The solubility parameters of described blocked polyisocyanates compound (B) is in specified range; The difference of the solubility parameters (SP1) of acrylic resin (A) and the solubility parameters (SP2) of blocked polyisocyanates compound (B) is in specified range.
Acrylic resin (A)
Used acrylic resin (A) is to contain the acrylic resin that specific primary hydroxyl is a crosslinking functionality in these decorations coating compositions, and it can and (c) obtain by the following monomer (a) and (b) of copolymerization:
(a) (methyl) acrylate of at least a hydroxyl by following formula (I) expression:
Wherein,
R 1Represent hydrogen or methyl and
R 2Represent C at least 4Uncle's hydroxyalkyl, C at least 4The organic substituent of primary hydroxyl polyoxyalkylene or following formula (II) expression
Figure A20081008349300082
Wherein, R 3Represent hydrogen or methyl, 1 is 2～5 integer, and especially 3～5 integer, and k is 1～7 integer, especially 2～6 integer;
(b) at least a vinyl monomer that contains carboxyl, sulfonic group or phosphate; With
(c) but at least a other copolyethylene monomer.
(a) (methyl) acrylate of hydroxyl:
R in the formula (I) 2Representative contains at least 4, preferred 4～12, especially the example of hydroxyl (methyl) acrylate (a) of uncle's hydroxyalkyl of 4～10 carbon atoms comprises (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) vinylformic acid 5-hydroxy pentane ester, (methyl) vinylformic acid 1-methyl-4-hydroxy butyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 1-methyl-5-hydroxy pentane ester, (methyl) vinylformic acid 7-hydroxyl heptyl ester, (methyl) vinylformic acid 8-hydroxyl monooctyl ester, (methyl) vinylformic acid 9-hydroxyl ester in the ninth of the ten Heavenly Stems and (methyl) vinylformic acid 10-hydroxyl ester in the last of the ten Heavenly stems.Wherein, from the curability of acrylic resin and the viewpoint of second-order transition temperature, preferred (methyl) vinylformic acid 4-hydroxy butyl ester.
R in the formula (I) 2Representative contains at least 4, and preferred 4～14, the example of hydroxyl (methyl) acrylate (a) of the primary hydroxyl polyoxyalkylenes of 4～10 carbon atoms especially comprises the polyalkylene oxide affixture of (methyl) acrylic acid hydroxy alkyl ester.Here, (methyl) acrylic acid hydroxy alkyl ester can be, for example, and (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate etc.Simultaneously, as polyalkylene oxide, that can mention has, for example, and the multipolymer of the multipolymer of polyethylene oxide, poly(propylene oxide), polybutylene oxide, polyethylene oxide and polybutylene oxide and poly(propylene oxide) and polyethylene oxide.Specific examples comprises BLENMER PE-90, PE-200 and the 55PET-400 (trade(brand)name) of NOF company.
Term " (methyl) acrylate ", used as this specification sheets, be meant acrylate or methacrylic ester, " (methyl) vinylformic acid " is meant acrylic or methacrylic acid, and " (methyl) acryl " is meant acryl or methacryloyl.
R in the general formula (I) 2Be example, comprise the 6-caprolactone or the gamma-butyrolactone affixture of (methyl) vinylformic acid 2-hydroxypropyl acrylate or (methyl) vinylformic acid 2-hydroxyl ethyl ester by hydroxyl (methyl) acrylate (a) of the organic substituent of general formula (II) representative.More particularly, can use Daicel ChemicalIndustries, the PLACCEL of Ltd. TMSeries monomers is as PLACCEL FM1, PLACCELFM2, PLACCEL FA2 and PLACCEL FM6.
Above-mentioned hydroxyl (methyl) acrylate (a) can use separately, or 2 kinds or multiple being used in combination.
The consumption of hydroxyl (methyl) acrylate (a) can be monomer (a) and (b) and (c) 20～60 quality % of total mass, preferred 25～55 quality %, especially 25～45 quality %.When the consumption of hydroxyl (methyl) acrylate (a) was less than 20 quality %, it is not enough that the curability of filming becomes, and this causes the performance of filming sometimes, and as hardness of film, deficiency or resurfacing agglomerability reduce.Otherwise when it surpassed 60 quality %, filming to have inferior water tolerance.
In acrylic resin (A), use 20～60 quality % hydroxyl (methyl) acrylate, when being converted into the hydroxyl value that hydroxyl (methyl) acrylate (a) contributed, approximately corresponding to 80～200mgKOH/g.Therefore, the hydroxyl value that hydroxyl (methyl) acrylate (a) is contributed acrylic resin (A) generally can be in 80～200mgKOH/g scope, special 90～180mgKOH/g, especially 110～180mgKOH/g.
(b) vinyl monomer
Vinyl monomer (b), used second component when promptly preparing acrylic resin (A) is that each molecule contains at least 1, preferred 1～12, the monomer of 1～8 carboxyl, sulfonic group or phosphate especially.
The example that contains carboxylic monomer comprises (methyl) vinylformic acid, fumaric acid, Ba Dousuan, methylene-succinic acid, methylene-succinic acid monomethyl ester, methylene-succinic acid monobutyl ester, toxilic acid and maleic anhydride, toxilic acid monomethyl ester, toxilic acid monobutyl ester and toxilic acid list octyl group ester.
Contain the monomeric example of sulfonic group and comprise vinyl sulfonic acid, vinylbenzenesulfonic acid and (methyl) vinylformic acid sulphur ethyl ester.
The monomeric example of phosphorous acidic group comprises acid phosphoric acid 2-(methyl) acryloxy ethyl ester, acid phosphoric acid 2-(methyl) acryloxy propyl diester, acid phosphoric acid 2-(methyl) acryloxy-3-chloro propyl diester and 2-(methyl) acryloxy ethylphenyl phosphoric acid.As the commodity of this class, can mention have KAYAMER PM21 (trade(brand)name, Nippon Kayaku Co., Ltd.) and Light EsterPM (trade(brand)name, Kyoeisha Chemical Co., Ltd.).
These vinyl monomers (b) can use separately, or 2 kinds or multiple being used in combination.
The consumption of vinyl monomer (b) can be 0.7～15 quality % of monomer (a) and (b) and combination quality (c), preferred 1～10 quality %, especially 2～6 quality %.When the consumption of vinyl monomer (b) was less than 0.7 quality %, the curability of the water-dispersion of acrylic resin (A) stability or decorations coating compositions can become not enough.Otherwise when it surpassed 15 quality %, the water tolerance of filming can reduce.
The consumption of 0.7～15 quality % vinyl monomer (b) is about 5～50mgKOH/g corresponding to the acid number of acrylic resin (A) in acrylic resin (A).Therefore the acid number of acrylic resin (A) generally can be in 5～50mgKOH/g scope, special 10～40mgKOH/g, especially 20～35mgKOH/g.
In acrylic resin (A), this class carboxyl, sulfonic group or the phosphate introduced by vinyl monomer (b) mainly make resin have water-dispersible, also play internal activator simultaneously when acrylic resin (A) and blocked polyisocyanates compound (B) are crosslinked.
(c) other vinyl monomer:
In preparation acrylic resin (A) used can with monomer (a) and (b) specific examples of other vinyl monomer (c) of copolymerization comprise those that mentioned in following (1)～(9):
(1) the hydroxyl monomer except that hydroxyl (methyl) acrylate (a): for example, (methyl) acrylic acid hydroxy alkyl ester is as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester and (methyl) vinylformic acid 3-hydroxy butyl ester.
With the hydroxyl monomer except that hydroxyl (methyl) acrylate (a) time, its consumption can be as follows: when making up with hydroxyl (methyl) acrylate (a), the hydroxyl value that makes acrylic resin (A) is generally in 110～200mgKOH/g scope, preferred 120～180mgKOH/g, especially 130～170mgKOH/g.
(2) (methyl) vinylformic acid and C 1-20, C especially 1-12The mono-esterification product of single hydroxyl alcohol, for example: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) isobornyl acrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid cetyl ester and (methyl) stearyl acrylate ester.
(3) styrene derivatives: for example, vinylbenzene, alpha-methyl styrene and Vinyl toluene.
(4) contain the epoxy group(ing) monomer: each molecule contains the compound of at least one glycidyl and at least one polymerizable unsaturated bond, and specific examples comprises (methyl) glycidyl acrylate, (methyl) allyl glycidyl ether and a glycidyl (methyl) acrylate.
(5) polymerisable unsaturated amides: for example, acrylamide, Methacrylamide, DMAA, N-methoxymethyl (methyl) acrylamide, N, N-dimethyl propyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, N-methylol (methyl) acrylamide and diacetone acrylamide.
(6) alkaline monomer: for example, dimethyl aminoethyl (methyl) vinylformic acid.
(7) other vinyl compound: for example, vinyl-acetic ester, propionate, vinylchlorid and versatic TMThe acid vinyl ester.Here, as versatic TMThe acid vinyl ester can be mentioned commodity Veo Va 9 and Veo Va 10 (trade(brand)name, Japan Epoxy Resin Co.) etc.
(8) polymerisable unsaturated nitrile: for example, vinyl cyanide and methacrylonitrile.
(9) contain the monomer (be included in hydroxyl (methyl) acrylate (a) those except) of polyoxyalkylene: for example, containing the molecular side chain end group is (methyl) acrylate of the polyethylene glycol groups of methoxyl group.As commercial examples, can use BLENMER PME-400, BLENMER PME-4000 (trade(brand)name, NOF Corporation) etc.When acrylic resin (A) has low acid number (content that is vinyl monomer (b) is few), be to improve the water-dispersion stability of acrylic resin, can contain the monomer that the molecular side chain end is the polyethylene glycol groups of methoxyl group with this.
Polymerisable other vinyl monomer of this class (c) can use separately, or 2 kinds or multiple being used in combination.
For guaranteeing to film satisfied curability and water tolerance and surface flatness, the hydroxyl value of acrylic resin (A) generally can be in 110～200mgKOH/g scope, preferred 120～180mgKOH/g, especially 130～170mgKOH/g; Acid number generally in 5～50mgKOH/g scope, special 10～40mgKOH/g, especially 20～35mgKOH/g.
Be the film performance of satisfaction guaranted, as acid resistance and coatingsurface slickness etc., the weight-average molecular weight of acrylic resin (A) generally also can be in 2,000～30,000 scope, and is preferred 3,000～17,000, and especially 4,000～15,000.
In this manual, " weight-average molecular weight " is the color atlas of measuring from gel permeation chromatograph, the value of being calculated based on the polystyrene standard molecular weight.Later in the production instance of Chu Xianing, the measurement of weight-average molecular weight gel permeation chromatograph HLC8120GPC (trade(brand)name, TosohCorporation) and TSKgel G-4000HXL, TSKgel G-3000HXL, TSKgelG-2500-HXL and TSKgel G-2000HXL (trade(brand)name, Tosoh Corporation) 4 pillars, carry out under following condition: mobile phase is a tetrahydrofuran (THF); Measuring temperature is 40 ℃; Flow rate is 1cm 3/ min, and detector is RI.
Consider the hardness of filming and the slickness of coating surface, the second-order transition temperature of acrylic resin (A) is preferably generally in-30～40 ℃ of scopes, especially-20 ℃～30 ℃.
In this manual, " second-order transition temperature " is to press JISK7121 (the transition temperature method of masurement of plastics) with DSC (differential scanning calorimeter), the value that records with 10 ℃/min temperature rise rate.In the production example of Chu Xianing, the measurement of second-order transition temperature behind 130 ℃ of dry 3h, is used SSC 5200 (trade(brand)name, Seiko Instru-ments ﹠amp in the tested sample that makes specified quantitative on the sample disc later; Electronics Ltd.) carries out as DSC.
Be preparation acrylic resin (A), can make hydroxyl (methyl) acrylate (a), vinyl monomer (b) but and other copolyethylene monomer (c) by being that the consumption of following scope carries out copolymerization with respect to monomer (a) and (b) and (c) total amount separately:
Hydroxyl (methyl) acrylate (a): 20～60 quality %, preferred 25～55 quality %, especially 25～45 quality %.
Vinyl monomer (b): 0.7～1 5 quality %, preferred 1～10 quality %, especially 2～6 quality %.
But other vinyl monomer (c) of copolymerization: 25～79.3 quality %, preferred 35～75 quality %, especially 49～73 quality %.
About monomer (a) and (b) and (c) polymerization, can be with known per se those, as solution polymerization process, mass polymerization, emulsion polymerization etc., with solution polymerization process for especially convenient.Solution polymerization process generally can be undertaken by comonomer (a) and (b) and mixture (c) in the presence of organic solvent and polymerization starter.As organic solvent commonly used, consider water-dispersible, preferred, for example, hydrophilic organic solvent is as alcohols, as Virahol; The ester class is as butylacetate; Gylcol ether or glycol ether ethers.As polymerization starter; can use those that use always; as Diisopropyl azodicarboxylate, benzoyl peroxide base, peroxidation two tert-pentyls, di-t-butyl peroxide, the caproic acid tertiary butyl-peroxy-2-ethyl ester, caproic acid tert-pentyl-peroxy-2-ethyl ester, withered rare hydroperoxide etc.; and in case of necessity; can use chain-transfer agent simultaneously, as 2 mercapto ethanol, n-octyl mercapto alcohol etc.
The copolymerization of acrylic resin (A) can or comprise the multistep polymerization method at least 2 steps with one-step polymerization method and carry out.In solution polymerization process, one-step polymerization comprises in the given time all knocks down the reactor that solvent exists to all monomer components and polymerization starter.And the multistep polymerization method is not to drop into all monomer components simultaneously, but monomer component is divided at least 2 parts and they are successively knocked down reactor.
From the water-dispersible that improves acrylic resin (A) with from the viewpoint of the water-dispersion stability of its decorations coating compositions of making, preferably with the multistep polymerization thing synthetic acrylic resins (A) that comprised at least 2 steps.
More particularly, preferably go on foot the acrylic resin that polymerizations obtain with good water-dispersion stability with 2, described 2 step polymerizations comprise, for example, the following step: at first polymerization does not contain or contains and seldom contains the monomeric monomer component of hydrophilic group, adds (input) then and contains the monomeric monomer component of hydrophilic group and do further polymerization.
Acrylic resin (A) can use separately, or 2 kinds or multiple being used in combination.
Blocked polyisocyanates (B)
The blocked polyisocyanates compound (B) that is used as linking agent in these decorations coating compositions is to obtain by seal the isocyanate group that each molecule contains the compound of at least 2 free isocyanate groups with end-capping reagent.
As polyisocyanate compound, can mention those that use always in the polyurethane preparation, for example, the derivative of aliphatic polyisocyante, alicyclic polyisocyanates, virtue-aliphatic polyisocyanate, aromatic polyisocyanate and these polyisocyanates (as the amido-containing acid ester base-, carbodiimide-, allophanate group-, urea groups-, biuret groups-, urethane diketone (urethodione) base-, urethane imines (urethoimine) base-, isocyanuric acid base-or oxazolidine ketone group-modified product).
The example of aliphatic polyisocyante comprises aliphatic diisocyanate, as ethylidene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, many two cyanates of pentamethylene, ten dimethylene diisocyanates, lysinediisocyanate, 1, the 2-trimethylene diisocyanate, 1,2-butylidene vulcabond, 2,3-butylidene vulcabond, 1,3-butylidene vulcabond, 2,4,4-or 2,2, the 4-trimethyl hexamethylene diisocyanate, two (the 2-isocyanate group ethyl) esters of fumaric acid, two (the 2-isocyanate group ethyl) esters of carbonic acid, n-caproic acid 2, the diisocyanate based methyl ester of 6-, 2, the diisocyanate based caproic acid 2-of 6-isocyanate group ethyl ester etc.; The aliphatics triisocyanate, as Methionin ester triisocyanate, 1,4,8-triisocyanate base octane, 1,6,11-triisocyanate base undecane, 1,8-is diisocyanate based-4-isocyanate group methyloctane, 1,3,6-triisocyanate base hexane, 2,5,7-trimethylammonium-1,8-is diisocyanate based-5-isocyanate group methyloctane etc.
The example of alicyclic polyisocyanates comprises alicyclic diisocyanate, as 1,3-cyclopentenes vulcabond, 1, the 4-cyclohexyl diisocyanate, 1, the 3-cyclohexyl diisocyanate, 3-isocyanic ester ylmethyl-3,5,5-3-methyl cyclohexanol based isocyanate (common name: isophorone diisocyanate), 4,4 '-methylene radical two (cyclohexyl isocyanate), methyl-2, the 4-cyclohexyl diisocyanate, methyl-2, the 6-cyclohexyl diisocyanate, 1,3-two (isocyanic ester ylmethyl) hexanaphthene, 1,4-two (isocyanic ester ylmethyl)-hexanaphthene, norbornene alkyl diisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond (hydrogenation MDI), the cyclohexylidene vulcabond, methyl cyclohexylidene vulcabond (hydrogenation TDI), two (2-isocyanate group ethyl)-4-cyclohexylidenes-1,2-dicarboxylic ester etc.; With alicyclic triisocyanate, as 1,3,5-triisocyanate basic ring hexane, 1,3,5-trimethylammonium isocyanate group hexanaphthene, 2-(3-isocyanate group propyl group)-2,5-two (isocyanic ester ylmethyl)-two ring (2.2.1) heptane, 2-(3-isocyanate group propyl group)-2,6-two (isocyanic ester ylmethyl)-two ring (2.2.1) heptane, 3-(3-isocyanate group propyl group)-2,5-two (isocyanic ester ylmethyl)-two ring (2.2.1) heptane, 5-(2-isocyanate group ethyl)-2-isocyanate group-3-(3-isocyanate group propyl group)-two ring (2.2.1) heptane, 6-(2-isocyanate group ethyl)-2-isocyanic ester ylmethyl-3-(3-isocyanate group propyl group)-two ring (2.2.1) heptane, 5-(2-isocyanate group ethyl)-2-isocyanic ester ylmethyl-2-(3-isocyanate group propyl group)-two ring (2.2.1) heptane, 6-(2-isocyanate group ethyl)-2-isocyanic ester ylmethyl-2-(3-isocyanate group propyl group)-two ring (2.2.1) heptane etc.
The example of virtue-aliphatic polyisocyanate comprises virtue-aliphatic vulcabond, as 1,3-or 1,4-xylylene diisocyanate or their mixture, ω, ω '-diisocyanate based-1,4-diethylbenzene, 1, tetramethyl xylylene diisocyanate) or their mixture 3-or 1,4-two (1-isocyanate group-1-methylethyl) benzene (common name:; And virtue-aliphatic triisocyanate, as 1,3,5-triisocyanate ylmethyl benzene etc.
The example of aromatic polyisocyanate comprises aromatic diisocyanate, as m-benzene diisocyanate, PPDI, 4,4 '-diphenyl diisocyanate, 3,3 '-dimethyl-4,4 '-diisocyanate based biphenyl, 3,3 '-dimethyl-4,4 '-diisocyanate based ditan, 1, the 5-naphthalene diisocyanate, 2,4 '-or 4,4 '-diphenylmethanediisocyanate (MDI) or their mixture, 2,4-or 2,6-tolylene diisocyanate or their mixture, 4,4 '-Tolylamine vulcabond, 4,4 '-diphenyl ether vulcabond, between-and right-isocyanate group phenyl sulfo group isocyanic ester etc.; Three aromatic isocyanate is as tritane-4,4 ', 4 "-triisocyanate, 1,3,5-triisocyanate base benzene and 2,4,6-triisocyanate base toluene; And the aromatics tetraisocyanate, as 4,4 '-ditan-2,2 ', 5,5 '-tetraisocyanate etc.
In addition, example as the polyisocyanic acid ester derivative, can mention the multiple derivative of above-mentioned polyisocyanate compound, as their dimer, tripolymer, biuret, allophanate, carbodiimide, urethane diketone (urethodion), urethane imines (urethoimine), isocyanuric acid ester, Ya An Ji oxadiazine diketone etc.
This class polyisocyanate compound can use separately or 2 kinds or multiple being used in combination.In these polyisocyanate compounds, preferred aliphat polyisocyanates, alicyclic polyisocyanates and their derivative, because the gained cured coating film has good ageing resistance, wherein especially preferred hexamethylene diisocyanate (HDI), its derivative, isophorone diisocyanate (IPDI) and derivative thereof.
Consider cover quality and water-dispersible, the number-average molecular weight of blocked polyisocyanates compound preferably generally is no more than 3,000, especially 300～2, and in 000 scope, especially 500～1,500.
In this manual, the number-average molecular weight of blocked polyisocyanates compound is the value of calculating based on the polystyrene standard molecular weight from the color atlas of measuring with gel permeation chromatograph.Later in the production example of Chu Xianing, the mensuration of number-average molecular weight gel permeation chromatograph HLC8120GPC (trade(brand)name, Tosoh Corporation) and TSKgel G-4000HXL, TSKgel G-3000HXL, TSKgel G-2500-HXL and TSKgel G-2000HXL (trade(brand)name, Tosoh Corporation) 4 pillars, carry out under following condition: mobile phase is a tetrahydrofuran (THF); Measuring temperature is 40 ℃; Flow rate is 1cm 3/ min and detector are RI.
End-capping reagent is the compound that temporarily seals free isocyanate groups, and be heated to the storing temperature of filming at isocyanic ester with the end-capping reagent sealing, for example, be not less than 100 ℃, when preferably being not less than 130 ℃, end-capping reagent disassociation produces free isocyanate groups again, they be easy to base resin in hydroxyl and so on react.
The example of end-capping reagent comprises phenols, as phenol, cresols, xylylol, nitrophenols, ethylphenol, hydroxy diphenyl, butylphenol, isopropyl-phenol, a basic phenol, octyl phenol, methyl hydroxybenzoate etc.; Lactan is as ε-Ji Neixianan, δ-Valerolactim, butyrolactam, azetidinone etc.; Fatty Alcohol(C12-C14 and C12-C18) is as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, lauryl alcohol etc.; Ether is as glycol monomethyl methyl ether, carbiphene, ethylene glycol monobutyl ether, diglycol monotertiary methyl ether, carbiphene, propylene glycol monomethyl ether, methoxyl group methyl alcohol etc.; Benzylalcohol; Glycolic acid; Glycolate is as glycolic acid methyl esters, glycolic acid ethyl ester, glycolic acid butyl ester etc.; Lactic acid; Lactate is as methyl lactate, ethyl lactate, n-Butyl lactate etc.; Alcohol is as methylolurea, methylol melamine, diacetone alcohol, vinylformic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester etc.; Oxime is as formamidoxime, amino second oxime, acetoxime, methyl ethyl ketoxime, diacetyl monoxime, benzophenone oxime, hexanaphthene oxime etc.; The active methylene group system is as dimethyl malonate, diethyl malonate, methyl aceto acetate, methyl acetoacetate, Acetyl Acetone etc.; Mercapto alcohol is as fourth mercapto alcohol, uncle's fourth mercapto alcohol, own mercapto alcohol, uncle's dodecane mercapto alcohol, 2-mercaptobenzothiazole, thiophene, methyl thiazolium phenol, ethylthiophene etc.; The acid acid amides is as Acetanilide, methoxyacetanilide, acettoluide, acrylamide, Methacrylamide, acetate acid amides, stearic amide, benzamide etc.; Imide is as succinimide, phthalic imidine, maleimide etc.; Amine is as diphenylamine, phenyl naphthyl amines, xylidine, N-phenyl xylidine, carbazole, aniline, naphthylamines, butylamine, dibutylamine, butyl phenyl amine etc.; Imidazoles is as imidazoles, 2-ethyl imidazol(e) etc.; Urea is as urea, thiocarbamide, ethylidene-urea, ethylene thiourea, diphenyl urea etc.; Carbamate is as phenyl N-phenylcarbamate; Imines is as piperazine, propylidene imines etc.; Disulphide (sulfite) is as sodium disulfide (sodium disulfite), curing potassium etc.; And azole compounds.As the example of azole compounds, that can mention has a pyrazoles or derivatives thereof, as pyrazoles, 3,5-dimethyl pyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethyl pyrazole, 4-nitro-3,4-bromo-3,3-methyl-5-phenylpyrazole etc.; The imidazoles or derivatives thereof is as imidazoles, benzoglyoxaline, glyoxal ethyline, 2-ethyl imidazol(e), 2-phenylimidazole etc.; And imidazolidine derivatives, as glyoxal ethyline quinoline, 2-benzylimidazoline etc.
In above-mentioned end-capping reagent, preferred azole compounds, as pyrazoles or pyrazole derivatives, since its good low-temperature curable and anti-jaundice, especially preferred 3.
Solubility parameters
As previously mentioned, water-based single-component paint of the present invention comprises acrylic resin (A) and at least a blocked polyisocyanates compound (B), the solubility parameters (SP1) of acrylic resin (A) is 9.30～11.20, the solubility parameters (SP2) of blocked polyisocyanates chemical combination (B) is 9.00～11.50, and the difference Δ SP (Δ SP=(SP1)-(SP2)) of solubility parameters (SP1) and solubility parameters (SP2) is in-0.80～1.50 scopes.
When the solubility parameters (SP1) of acrylic resin (A) surpassed 11.20, high polarity can cause the water-dispersible of blocked polyisocyanates compound (B) to reduce or the acid resistance of filming that forms reduces.Otherwise when less than 9.30 the time, low polarity can cause that the water-dispersible of blocked polyisocyanates compound reduces.
When the solubility parameters (SP2) of blocked polyisocyanates compound (B) surpasses 11.50 because high polarity, the water tolerance of filming of forming or acid resistance or can reduce based on the water-dispersible of acrylic resin (A).Otherwise when less than 9.00 the time, low polarity can reduce the water-dispersible based on acrylic resin (A).
In addition, when the difference Δ SP (Δ SP=(SP1)-(SP2)) of the solubility parameters (SP1) of acrylic resin (A) and the solubility parameters (SP2) of blocked polyisocyanates compound less than-0.80 the time, because the low polarity of acrylic resin (A), the water-dispersible of blocked polyisocyanates compound (B) can reduce, and the consistency of component (A) and component (B) also can reduce, thereby impairs the slickness of filming.Otherwise when Δ SP value surpassed 1.50, the consistency of component (A) and component (B) reduced, and this can cause film relatively poor surface flatness or the dispersive ability of reduction blocked polyisocyanates compound in the water that contains acrylic resin (A) of forming.
Therefore, in water-based single-component paint of the present invention the solubility parameters (SP1) of used acrylic resin (A) preferably in 9.30～11.20 scopes, special 9.50～11.00, especially 9.70～10.60.The solubility parameters (SP2) of blocked polyisocyanates compound (B) is also preferably in 9.00～11.50 scopes, and is special 9.20～10.50, and especially 9.20～10.00.
Consider water-dispersible and the surface flatness of filming, the solubility parameters (SP1) of preferred acrylic resins (A) drops in-0.80～1.50 scope with the difference Δ SP of the solubility parameters (SP2) of blocked polyisocyanates compound (B), especially-0.20～1.30, especially 0.50～1.20.
These solubility parameters values of acrylic resin mentioned in this article (A) and blocked polyisocyanates compound (B) are with the practical measurement method---heterometry is measured easily, and with following K.W.Suh, J.M.Corbett Equation for Calculating (Journal of Applied Polymer Science, 12,2359,1968):
SP = V H · δ H + V D · δ D V H + V D
Solubility parameters (SP) is the value by following mensuration: 0.5g (solids content) exsiccant acrylic resin or blocked polyisocyanates compound are placed on the high beaker that internal diameter is 50mm (in the capacity=100ml) and be dissolved in the 10ml acetone.At 25 ℃, in this solution, drip normal hexane while stirring, till No. 4 words that do not see from the beaker top on a slice newspaper that is placed under the beaker, resolvable limit is designated as cloud point.Read out in the titer H (ml) of cloud point.Equally, replace normal hexane that acetone soln is advanced in the deionized water titration, read out in the titer D (ml) of cloud point.The V that calculates according to following formula from these titers H, V D, δ HAnd δ DValue is for advancing aforementioned K.W.Suh, J.M.Corbett equation.The SP value of solvent is as follows: normal hexane, 7.24; Deionized water, 23.43; And acetone, 9.75.
V H＝H/(10+H)
V D＝D/(10+D)
δ H＝9.75×10/(10+H)+7.24×H/(10+H)
δ D＝9.75×10/(10+D)+23.43×D/(10+D)
In water-based single-component paint of the present invention, the preferred blending ratio of acrylic resin (A) and blocked polyisocyanates compound (B) will make the isocyanate group in the blocked polyisocyanates compound (B) and the equivalence ratio of the hydroxyl in the acrylic resin (A), i.e. (NCO/OH), generally drop in 0.5～1.0 scope, special 0.6～0.9, especially 0.7～0.9.Less than 0.5 o'clock, the curability of main body coating reduced in equivalence ratio, and surpassed at 1.0 o'clock, and the amount of hydroxyl groups of staying film coated surface can reduce, and the agglomerability of film and no sand resurfacing can reduce.
According to the preferred blending ratio between acrylic resin (A) and the blocked isocyanate compounds (B), acrylic resin (A) generally can account for 50～75 quality %, special 55～70 quality %, especially 60～70 quality %; And blocked polyisocyanates compound (B) can account for 25～50 quality %, special 30～45 quality %, and 30～40 quality % especially are that 100 quality % calculate with the combined solid content of these 2 kinds of components.
It is the additive-crosslinking agent that decorations coating compositions of the present invention also can contain melmac.The example of melmac comprises the methylol melamine, as dihydroxymethyl melamine, trishydroxymethyl melamine, tetra methylol melamine, five hydroxymethyl melamine and hexamethylol melamine; The alkyl etherificate or the condensation product of these methylol melamines; And the condensation product of alkyl etherificate methylol melamine.The alkyl etherificate of methylol melamine can be used MHA, as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, ethylhexyl alcohol etc., carries out with known method own.
As melmac, also can use the commercially available prod.That can mention has, for example, CYMEL 303, CYMEL 323, CYMEL 325, CYMEL 327, CYMEL 350, CYMEL 370, CYMEL 380, CYMEL 385, CYMEL 212, CYMEL 251, CYMEL 254 and the MYCOAT 776 of CytecIndustries manufacturing; REGIMIN 735, REGIMIN 740, REGIMIN 741, REGIMIN 745, REGIMIN 746 and REGIMIN 747 that Monsanto Chemical Co. makes; SUMIMALM55, SUMIMAL M30W and SUMIMAL M50W that Sumitomo Chemicals makes; U-VAN20SB, U-VAN20SE-60, U-VAN28-60 (being trade(brand)name entirely) that Mitsui Chemicals makes.
When using melmac, its blending ratio preferably, the combined solid content for per 100 mass parts acrylic resins (A) and blocked polyisocyanates compound (B) is no more than 15 mass parts, especially 0～10 mass parts.
In coating composition of the present invention, use organo-tin compound and/or bismuth compound as curing catalysts.The example of organo-tin compound comprises the aliphatic series or the aromatic carboxylic acid salt of dialkyl tin, as dibutyl tin laurate, two lauric acid dioctyl tins, dibutyltin diacetate, phthalic acid dibutyl tin, dibenzoic acid dioctyl tin and dibenzoic acid dibutyl tin; The aliphatic series of monoalkyltin or aromatic carboxylic acid salt are as the trioctylphosphine Monobutyltin; And distannoxane, as tetra-n-butyl-1,3-diacetoxy distannoxane.
The example of bismuth compound comprises inorganic bismuth compound, as bismuth oxide, bismuth hydroxide, alkaline carbonic acid bismuth, Bismuth trinitrate and bismuth silicate.
As bismuth compound, can also be with the organic acid that is obtained by the reaction of organic acid and the above-mentioned inorganic bismuth compound bismuth compound of deriving, described organic acid such as acetate, sad, glycolic acid, R-Glyceric acid, lactic acid, dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid, tartrate, toxilic acid, tartronic acid, dihydroxysuccinic acid, trihydroxy-succsinic acid, Methylpropanedioic acid, phenylformic acid, Acidum Citricum etc.In above-mentioned organic acid is derived bismuth compound, preferred especially three Bismuth Octoates that obtained by bismuth hydroxide and sad reaction.
In these decorations coating compositions, for per 100 mass parts acrylic resins (A) and blocked polyisocyanates compound combined solid content, as the organo-tin compound of catalyzer and/or the preferred content of bismuth compound generally is 0.01～10 mass parts, preferred 0.05～8 mass parts, especially 0.05～1 mass parts.
In case of necessity, these decorations coating compositions also can contain the UV absorption agent.The example of UV absorption agent comprises triaizine compounds and benzotriazole cpd, for improving heat-resisting flavescence, and preferred especially triaizine compounds.
As triaizine compounds, that can mention has, for example, 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-and the 5[(hexyl) the oxygen base]-phenol is (for example, TINUVIN 1577FF, trade(brand)name, Ciba SpecialtyChemicals Inc.), 2-[4-[6-(2-hydroxyl-3-dodecyl oxygen base propyl group) oxygen base]-the 2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazine and 2-[4-[6 (2-hydroxyl-3-dodecyl oxygen base propyl group) oxygen base]-the 2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazine (for example TINUVIN 400, trade(brand)name, Ciba Specialty Chemicals Inc.), 2,4-two (2, the 4-3,5-dimethylphenyl)-6-(2-hydroxyl-4-iso-octyl oxygen base phenyl)-s-triazine (for example, TINUVIN 411L, trade(brand)name, Ciba Specialty Chemicals Inc.), 2,4-two (2, the 4-3,5-dimethylphenyl)-6-(2-hydroxyl-4-octyl group oxygen base phenyl)-1,3, the 5-triazine (for example, CYAGARD UV1164L, trade(brand)name, MitsuiCytec K.K.) mixture etc.
The example of benzotriazole cpd comprises 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-[2 '-hydroxyl-3 ', 5 '-two-(1, the 1-dimethyl benzyl) phenyl]-the 2H-benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-two-tert-butyl-phenyl] benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-the 5-chlorobenzotriazole, 2-(2 '-hydroxyl-3,5 '-diisoamyl phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole or the like.
These UV absorption agents can use separately, or 2 kinds or multiple being used in combination.
For the combined solid content of per 100 mass parts acrylic resins (A) and blocked polyisocyanates compound (B), the content of UV absorption agent generally can be 0.1～10 weight part, preferred 0.5～5 mass parts, especially 0.8～3 mass parts.
In case of necessity, decorations coating compositions of the present invention can also with photostabilizer, carry out blend as the hindered amine photostabilizer of deriving, the specific examples of this class photostabilizer comprises two (2,2 ', 6,6 '-tetramethyl--4-piperidyl) sebate, 4-benzoyloxy-2,2 ', 6,6 '-tetramethyl piperidine etc.These photostabilizers can use separately or 2 kinds or multiple being used in combination.
During with this class photostabilizer, for the combined solid content of per 100 mass parts acrylic resins (A) and blocked isocyanate compounds (B), the consumption of photostabilizer generally can be 0.1～10 mass parts, preferred 0.5～5 mass parts, especially 0.8～3 mass parts.
Other component
If necessary, water-based single-component paint of the present invention can also resinous component, as vibrin, urethane resin etc.; Additive is as rheology control agent, surface conditioner, deaerating agent, antioxidant etc.; And pigment, as tinting pigment, metallic pigment, luster pigment, charge agent etc.When coating with lacquer as transparent decorations, can in the scope of not damaging the transparency of filming substantially, use above-mentioned additive and pigment with decorations coating compositions of the present invention.
The present invention adorns the preparation and the application of coating compositions
Water-based single-component paint of the present invention can be prepared as follows: acrylic resin (A) and blocked polyisocyanates compound (B), used optional components in case of necessity, all add water-bearing media as catalyzer, UV absorption agent, photostabilizer etc., as water, and mix, so that they are evenly dispersed in the medium.Mix and disperse preferably by with in the neutralizing agent and the method for acrylic resin (A) carry out, to improve its water-dispersible.When mixing and disperse, if necessary, also can improve dispersibility with emulsifying agent simultaneously.
The example of available neutralizing agent comprises the oxyhydroxide of basic metal or alkaline-earth metal, as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide and hydrated barta; Ammonia; Uncle's monoamine compound is as ethamine, propylamine, butylamine, hexahydroaniline, monoethanolamine, Yi Bingchunan, neopentyl alcohol amine, 2-aminopropanol, 3-aminopropanol and 2-amino-2-methyl propyl alcohol; The secondary monoamine compound is as diethylamine, dibutylamine, diethanolamine, dipropanolamine, diisopropanolamine (DIPA), N-Mono Methyl Ethanol Amine, N-ehtylethanolamine and N-methyl isopropyl hydramine; Uncle's monoamine compound is as triethylamine, Tributylamine, dimethylethanolamine, diethylethanolamine, methyldiethanolamine, dimethylaminoethanol and trolamine; Polyamine compounds is as ethylene diamine, diethylenetriamine, hydroxyethyl aminoethyl, ethylamino ethamine and methylamino propylamine; With pyridine, morpholine etc.Wherein preferred with uncle's monoamine compound, secondary monoamine compound, uncle's monoamine compound and polyamine compounds.
The consumption of neutralizing agent is not particularly limited, but can suitably select where necessary.And from improving the viewpoint of dispersion stabilization, for the acidic group total amount in amount acrylic resin (A), preferred neutralizing agent is generally with 0.6～1.2 equivalent, special 0.7～1.1 equivalent.
When preparation decorations coating compositions of the present invention, acrylic resin (A) and blocked polyisocyanates compound (B) generally mix and are dispersed in the organic solvent with the solution form also preferably removes organic solvent as much as possible with the method for underpressure distillation and so on from decorations coating compositions of the present invention, to reduce its VOC content.For control foaming in the step that removes organic solvent in method, can suitably add deaerating agent with underpressure distillation and so on.
The VOC content of water-based single-component paint of the present invention preferably is generally 0～300g/l, special 0～250g/l, especially 0～150g/l.In this manual, " VOC " is meant that The World Health Organization (WHO) ranges the volatile organic compounds of " high volatile volatile organic compound " and " volatile organic compounds ".
In thus obtained water-based single-component paint of the present invention, the average particle size particle size of preferred existing discrete particles generally in 100～150nm scope, special 100～400nm, especially 100～300nm.In these decorations coating compositions, blocked polyisocyanates compound (B) and used in case of necessity hydrophobic optional components are dispersed in the water as discrete particles, and acrylic resin (A) plays dispersion medium.When the average particle size particle size of discrete particles surpassed 500nm, the package stability of these decorations coating compositions reduced, so that impairs the slickness of filming, so the big average particle size particle size of this class is unfavorable.Otherwise when particle size during less than 100nm, the viscosity of decorations coating compositions increases, and the solids concn of decorations lacquer can reduce, and this also is unfavorable.
In this manual, the average particle size particle size that is present in the discrete particles in the water-based single-component paint be test sample decorations coating compositions is dispersed in the deionized water back with submicroscopic particle size distribution metering facility 20 ℃ of values that record.About this class sub-micro spectators particle size metering facility, can with on the market existing those, as COULTER N4 type (trade(brand)name, Beckman Coulter, Inc.).
When using, water-based single-component paint of the present invention, where necessary, preferred usually its viscosity of regulating is as follows: be diluted to deionized water, 20 ℃ of measurements, be generally 15～60s by No. 4 Ford cup viscometers, special 20～50s.In this case, solids concn preferably in 40～60 quality % scopes, special 45～55 quality %.Solids concn is filmed and is tended to more crease easily during less than 40 quality %.On the other hand, when surpassing 60 quality %, observe the tendency that high viscosity or water-dispersible reduce.
Consider water-dispersion stability, the pH value of water-based single-component paint of the present invention also preferably generally in 6.0～8.5 scopes, special 6.5～8.0.In the production example of Chu Xianing, the measurement of pH value is carried out with pH meter later.About pH meter, can use, for example, F-22 (trade(brand)name, HoribaSeisakusho).
In order to form cover and to film various will being coated with on the part, water-based single-component paint of the present invention can be coated with as air spray finishing, airless spraying process, rotary-atomizing coating method or similar approach with known method itself.When coating, also can apply static.Coating thickness with the cured film opinion, generally can be 20～50 μ m, preferred 25～45 μ m.The curing of filming can be implemented as follows: generally at about 120 ℃～about 170 ℃, preferably at about 130 ℃～about 170 ℃, heat about 10～40min.Heating can be carried out with method known per se, and for example, drying oven is as hot-air furnace, electric furnace, infrared drying oven etc.
Preferably carried out preheating before above-mentioned being heating and curing earlier, with the medium in the volatilization decorations coating compositions, as water or organic solvent, and oven dry is filmed.Preheating is generally carried out about 3～30min at about 50～about 100 ℃.By preheating, the solids concn in filming preferably rises at least 80 quality %.
The multilayer film forming method
Utilize water-based single-component paint of the present invention, can form performance and outward appearances such as curability, hardness of film, acid resistance and scratch resistance on applied object, as surface flatness, all good films.And, because water-based single-component paint of the present invention is also very good aspect the blocked polyisocyanates dispersion stabilization, so can be widely used as water-based paints.It especially is convenient to as the transparent decorations lacquer that forms the cover Clear coating.
Therefore, according to the present invention, the multilayer film forming method is provided, it is included in wants successively to be coated with on the coated object one deck priming paint and layer of transparent decorations lacquer at least at least, to form multilayer film, it is characterized in that being coated with water-based single-component paint of the present invention as the transparent decorations lacquer of outermost layer cover.
Applied object is not particularly limited, but preferred, for example, steel plate is as cold-rolled steel sheet, steel plate galvanized, galvanized alloy steel plate, stainless steel plate and tin plate; The metal base is as aluminium sheet and aluminium alloy plate; With various plastics.They also can be various vehicles, the car body of the container carrier that constitutes as automobile, two-wheel car with by them.
The coated article body also can be to handle through certain surface.As phosphatizing, chromate treating or the metal base of composite oxides processing or the metallic surface of car body.As the object that can use multilayer film forming method coating of the present invention, preferred especially car body and parts thereof.
For these coated article bodies, in case of necessity can first primer coating (as cationic electrodeposition coating), and according to circumstances, can be coated with other coating, as inter coat.
More specifically, energy usefulness, for example, following method a-c coats with lacquer as the transparent decorations of cover with water-based single-component paint of the present invention therein as multilayer film forming method of the present invention:
Method a:The multilayer film forming method of 2-coating system, wherein the transparent decorations of priority primer coating and cover coat with lacquer on applied object, to form multilayer film;
Method b:The multilayer film forming method of 3-coating system, wherein priority primer coating, the clear lacquer and the transparent decorations of cover coat with lacquer on applied object, to form multilayer film;
Method c:The multilayer film forming method of 3-coating system wherein successively is coated with the transparent decorations lacquer of the first road priming paint, the second road priming paint and cover, to form multilayer film on applied object.
Explain each method among the multilayer film forming method a-c in more detail below.
In method a-c, priming paint and transparent decorations lacquer can be coated with methods such as air spray finishing, airless spraying process, rotary-atomizing coatings.When these methods of enforcement, can apply static if necessary.
In above method a, can be with known priming paint itself as priming paint, preferably be used for being coated with the colored primer composition of body of a motor car etc. simultaneously.
The colored primer composition can be organic solvent based or aq. type, comprises base resin, linking agent and pigment (for example, tinting pigment, effect pigment etc.).From the viewpoint of low VOC content, preferred water base coating compositions.
About base resin, can use, for example, and at least a acrylic resin, Vinylite, vibrin, Synolac, urethane resin etc., they contain crosslinkable functionality, as hydroxyl, epoxy group(ing), carboxyl, alkoxysilyl or similar group.As linking agent, can use, for example, at least a alkyl etherificate melmac, urea resin, guanamine resin, polyisocyanate compound, blocked polyisocyanates compound, epoxy compounds, carboxylated compound etc.This class base resin and linking agent with respect to the preferable amount of 2 kinds of combination of components amounts are: base resin accounts for 50～90 quality % and linking agent accounts for 10～50 quality %.
The above-mentioned priming paint of coating with the cured coating film opinion, is generally about 10～50 μ m to thickness on the coated article body.The solidifying priming paint that has been coated with is as follows: generally at about 100～about 180 ℃, preferred about 120～about 160 ℃ of about 10～40min of heating perhaps do not solidify but allow at room temperature to treat several minutes or at about 40～about 100 ℃ of about 1～20min of preheating.
Then water-based single-component paint of the present invention is applied to thickness as the transparent decorations lacquer of cover,, is generally about 20～50 μ m, heat it then, solidify multilayer film to form with the cured coating film opinion.Heating is preferably generally at about 120～about 170 ℃, and preferred about 130～about 170 ℃ are carried out about 10～40min.
In aforesaid method, all on uncured bottom coating the transparent decorations of coating cover lacquer and solidify the situation that this bilayer films simultaneously and be referred to as 2-coating-1-baking systems.And, be called 2-coating-2-baking systems when being coated with priming paint and, being coated with the transparent decorations lacquer of cover then and solidifying these transparent decorations when coating with lacquer by being heating and curing.
In method b, can make priming paint with being similar to those paint base compositions of being explained among the method a.The clear lacquer is not particularly limited, as long as it can form transparent coating, and energy usefulness, for example, from priming paint known per se, leave out the coating compositions that major part or whole pigment are obtained.As the transparent decorations lacquer of cover, use water-based single-component paint of the present invention.Also can be with water-based single-component paint of the present invention as the clear lacquer.
Be similar to method a, in method b, priming paint is applied on the applied object, by being heating and curing it, or not solidifying but at room temperature treated several minutes or preheating, the transparent decorations of coating coat with lacquer thickness on bottom coating then, with the cured coating film opinion, general about 10～50 μ m are then at about 100～about 180 ℃, preferred about 120～about 160 ℃ solidify about 10～40min, or at room temperature place several minutes or preheating but do not have curing schedule.Then, be coated with water-based single-component paint of the present invention as the transparent decorations lacquer of cover, its thickness, with the cured coating film opinion, general about 20～50 μ m, similar with method a then, heat it, to form multilayer film.
In the above, when being coated with priming paint but do not make it to solidify, but paint transparent paint but do not solidify thereon is coated with the transparent decorations lacquer of cover then thereon, when solidifying this 3 coating film then simultaneously, adopts 3-coating-1-baking systems by heating.Keep uncured and heat simultaneously and solidifies at undercoat, be coated with then and when solidifying the cover Clear coating, employing 3-coating-2 baking systems with thereon Clear coating of coating.Further, when after being coated with separately, being heating and curing respectively for these 3 layers, adopt 3-coating-3-baking systems.
In method c, those paint base compositions that can be explained in a) with the method that is similar to are as the first road priming paint.Because the second road priming paint will be coated on the surface that has been coated with the first road priming paint, generally uses the low power of the covering colored primer composition that will see through the visible first road undercoat tone of the second road bottom coating as the second road priming paint.
Be similar to method a, in method c, the coating first road priming paint is heating and curing it on applied object, or do not solidify and stay treat under the room temperature several branch kinds or preheating it, on the first way bottom coating, be coated with second priming paint then to thickness, with the cured coating film opinion, be generally about 10～50 μ m, then at general about 100～about 180 ℃, preferred about 120～about 160 ℃ solidify 10～40min, or at room temperature placed several minutes or preheating and do not have a curing schedule.Be coated with water-based single-component paint of the present invention then and coat with lacquer thickness as the transparent decorations of cover, with the cured coating film opinion, be generally 20～50 μ m, the situation that is similar to method a then heats it, to form multilayer film.
In the above,, be coated with the second road priming paint then thereon but do not solidify it, be coated with the transparent decorations lacquer of cover then thereon, when solidifying this 3-coating film then simultaneously, adopt 3-coating-1-baking systems when being coated with the first road priming paint but not by being heating and curing.Keep at the first road priming paint and not solidify, heat simultaneously and solidifies with the coating second road priming paint thereon then, be coated with then and when solidifying the transparent decorations lacquer of cover, employing 3-coating-2-baking systems.In addition, when 3 layers each when its coating post-heating solidifies, adopt 3-coating-3-baking systems.
According to the present invention, the multilayer film that comprises the following step forming method also is provided: coated heat solidity water-based paints composition is as priming paint on applied object, coating water-based single-component paint of the present invention coats with lacquer as transparent decorations on uncured coatingsurface, and solidifies this undercoat and Clear coating simultaneously.This method wherein uses water base colored primer composition as priming paint corresponding to aforesaid method a, bakes big vast system with 2-coating-1-and carries out and be heating and curing.
Embodiment
More specifically explain the present invention below with reference to operation embodiment and comparative example, should be understood that to the invention is not restricted to these.Hereinafter " umber " and " % " without exception based on quality, the coating thickness after coating thickness refers to solidify without exception.
The preparation of acrylic resin (A)
Production example 1
In being equipped with the 4-neck flask of heater device, agitator, thermometer and reflux exchanger, drop into 30 parts of propylene glycol list propyl ethers, temperature rises to 145 ℃ in following bottle of logical nitrogen gas stream then.Stop supplies nitrogen also, as the fs, in 4 hours, in this flask, be added dropwise to 15 parts of vinylbenzene, 10 parts of n-butyl acrylates, 18 parts of Propenoic acid, 2-methyl, isobutyl esters, 13 parts of vinylformic acid 4-hydroxy butyl esters, 12 parts of PLACCEL FA-2,7 parts of methacrylic acid 2-hydroxyl ethyl esters and 3.0 parts of di-t-butyl peroxides.Keep reaction system 30min again under uniform temp.Then, as subordinate phase, in 30min, drip 6 parts of Propenoic acid, 2-methyl, isobutyl esters, 6 parts of vinylformic acid 4-hydroxy butyl esters, 6 parts of PLACCEL FA-2,3 parts of methacrylic acid 2-hydroxyl ethyl esters, 4 parts of vinylformic acid and 1.0 parts of di-t-butyl peroxides, ageing 1h under uniform temp then.Then, under reduced pressure boil off solvent, rise at least 95% up to solids concn.With 38 parts of methylethylketones dilution residues, obtain solids content and be 70% acrylic resin (A-1) solution.The hydroxyl value of gained acrylic resin (A-1) is 147mgKOH/g thus, and acid number is 31mgKOH/g, and weight-average molecular weight is 10,000, the SP measured value be 10.30 and Tg be 0 ℃.
Production example 2～15
With the parent material shown in the table 1, obtain acrylic resin (A-2)～(A-15) with the method that is similar to production example 1.
Table 1 has provided the composition of parent material, the solids content and the performance of acrylic resin (A-1)～(A-15).
Figure A20081008349300271
The preparation of blocked polyisocyanates compound (B)
Production example 16
In being equipped with the 4-neck flask of agitator, heating installation, cooling apparatus and pressure reducer, drop into 250 parts of SUMIDUR N3300 (annotating 1)With 125 parts of methylethylketones, and be heated to 30 ℃.In 2h, add 126 parts of 3 then while stirring gradually, and under agitation make reaction mixture reaction in 30 ℃, till detecting less than free isocyanate groups with infrared spectrophotometer.Behind the reaction end, obtain solids content and be the solution of 70% blocked polyisocyanates compound (B-1).The SP observed value of gained blocked polyisocyanates compound (B-1) is 9.33, NCO content be 14.4% and number-average molecular weight be 1,000.In this manual, " NCO content " is meant the NCO base unit weight (%) in the solids content of per 100 mass parts resins.
(annotating 1) SUMIDUR N3300: trade(brand)name, Sumika Bayer Urethane Co., Ltd., hexamethylene diisocyanate.
Production example 17
In being equipped with the 4-neck flask of agitator, heating installation, cooling apparatus and pressure reducer, drop into 272 parts of hexamethylene diisocyanates and 214 parts of methylethylketones, be heated to 60 ℃.In 1h, add 169 parts of methyl ethyl ketoximes then while stirring gradually.Under 60 ℃, make reaction continue 2h then, add 59 parts of TriMethylolPropane(TMP)s then gradually, in order to avoid temperature is raised to 70 ℃ or higher.Make to be reflected at 60 ℃ of continuation under agitation, till detecting less than free isocyanate groups with infrared spectrophotometer.Behind the reaction end, obtain solids content and be the solution of 70% blocked polyisocyanates compound (B-2).The SP observed value of gained blocked polyisocyanates compound (B-2) is 12.19, NCO content be 16.4% and number-average molecular weight be 950.
The preparation of water-based single-component paint
Embodiment 1
Stir and mix 88.6 parts of acrylic resin (A-1) solution and 54.4 parts of blocked polyisocyanates (B-1) solution (NCO/OH=0.8) with rotary agitator blade (DESPA MH-L, trade(brand)name, Asada Iron Works Co.Ltd.).Under further stirring, successively add 1 part of bitter almond oil camphor, 1 part of NEOSTANN U-100 then by described order (annotating 2), 1.4 parts of TINUVIN 1130 (annotating 3)With 1 part of SANOLLS-292 (annotating 4)And mix.Add 3.05 parts of dimethylaminoethanols (it is 1.0 that its amount will make the neutralization equivalent of carboxyl and amine) then gradually and continue to stir and 5min.Carry out water-dispersion by in this system, dripping 101 parts of deionized waters gradually then, to produce uniform dispersion.
Thus obtained water dispersion is added the 4 neck flasks that are equipped with agitator, well heater, water cooler and pressure reducer and under 50 ℃ and decompression, remove and desolvate, desolvate and water with distillation.When distillation volume when reaching 60 parts, stop decompression and desolventize step, and allow the residue cool to room temperature.Add more deionized water, with the viscosity adjustment of product to when measuring for 20 ℃, being 30s with No. 4 Ford cup viscometers, obtain the 1# water-based single-component paint.The solids content of this 1# water-based single-component paint is 50%, and average particle size particle size is 220nm.
(annotating 2) NEOSTANN U-100: trade(brand)name, Nitto Kasei Co., dibutyl tin laurate
(annotating 3) TINUVIN 1130: trade(brand)name, Ciba Specialty Chemicals Co., the benzotriazole-UV absorption agent of deriving
(annotating 4) SANOL LS-292: trade(brand)name, Sankyo Lifeteh Co., the hindered amine-photostabilizer of deriving.
Embodiment 2～13 and comparative example 1～11
With the parent material shown in table 2 and 3, obtain 2#～24# water-based single-component paint with the method that is similar to embodiment 1.Blocked isocyanate compounds in the table 2 and 3 (B-3) (annotating 5)With NEOSTANN U-600 (annotating 6)Characteristics as follows:
(annotate 5) blocked polyisocyanates compound (B-3): TPA-B80E (trade(brand)name, AsahiKaseiChemicals Co., the isocyanurate compound of the hexamethylene diisocyanate that isocyanate group has been sealed by methyl ethyl ketoxime; Solids content is 80%; NCO content is 15.6%).Its SP observed value is 11.45.
(annotating 6) NEOSTANN U-600: trade(brand)name, Nitto Kasei Co., the solution of three Bismuth Octoates (active principle, 57%).
After viscosity adjustment, measure solids content, VOC content and the average particle size particle size of each water-based single-component paint, and with following method test package stability.The decorations coating compositions of making among the comparative example 4,9 and 10 (17#, 22# and 23# water-based single-component paint) shows bad water-dispersible, and can not get their water dispersion, thereby can not estimate them.
The solids content (%) of decorations coating compositions: after viscosity adjustment, be that to measure each water-based single-component paint of about 2g on the aluminium dish of 5cm as follows at diameter: fully spread on the whole aluminium dish, at 110 ℃ of dry 1h, calculate solids content (%) from starting weight and dry back weight.
VOC content (g/l): after viscosity adjustment, the VOC content of each water-based single-component Clear paint (is used the proportion agar diffusion method from its proportion, pressing JIS K-5400 4.6.2 measures), water-content (the automatic water-content determinator of the commodity KF-100 by name that makes with MitsubishiChemicals Co., measure with the KarlFischer method) and the solids content of coating, press following formula (1) calculating:
VOC content (g/l)={ [100-(S+W)] * ρ }/[100-(w * ρ)] (1)
In formula (1), S represents the solids content (%) of coating, and W represents the water-content (%) of coating, and ρ represents the proportion (g/l) of coating.
The average particle size particle size of coating (nm): after viscosity adjustment, disperse each water-based single-component paint with deionized water, its average particle size particle size (nm) COULTER N4 type (trade(brand)name, BeckmanCoulter, Inc., submicroscopic particle size distribution determinator) 20 ℃ of mensuration.
Package stability: after viscosity adjustment, each water-based single-component paint was stored 10 days at 40 ℃, estimated its state according to following criterion then:
Zero: do not observe viscosity variation or precipitation, good
Zero △: observe small amount of precipitate, but when stirring, restore
△: observe small amount of precipitate, also can not restore even stir
*: because of being separated appears in precipitation, stir and also can not restore
Table 2 and 3 has provided solids content, the VOC content of poor, the coating of the component of each water-based single-component paint and composition (solids content umber), neutralization equivalent, NCO/OH ratio, acrylic resin performance, SP value, SP, the average particle size particle size and the package stability evaluation result of coating.
The preparation of test plate (panel) 1
Prepare test plate (panel) with each water-based single-component paint of resulting 1#～24# among embodiment 1～13 and the comparative example 1～11.(, can not make test plate (panel) because of making the decorations coating compositions as for comparative example 4,9 and 10 (17#, 22# and 23# water-based single-component paint).)
With cation electrophoretic paint (ELECRON GT-10, trade(brand)name, Kansai Patent Co.) electrophoretic painting is through cold rolling and steel plate (the PALBOND#3020 phosphoric acid zinc impregnation, trade(brand)name, NipponParkeriz-ing Co.) to thickness be 20 μ m, then at 170 ℃ of 30min that are heating and curing, to form electrocoating film.Be coated with organic solvent based inter coat (AMILAC TP-65-2 in the overhead gas blowout of electrocoating film, trade(brand)name, Kansai Paint Co., automobile is with vibrin-melmac type inter coat) to thickness be 35 μ m, stay under the room temperature and place 7min, at 140 ℃ of 20min that are heating and curing, film with in the middle of forming.
On filming in this centre, the coating automobile is 15 μ m with acrylic resin-melmac type water-based primer (WBC713T#1E7, trade(brand)name, Kansai Paint Co.) to thickness, stays to treat 5min under the room temperature and at 80 ℃ of preheating 10min.On this uncured undercoat, the 1# of gained～24# water-based single-component paint to each thickness is 35 μ m among separate application embodiment and the comparative example, stays under the room temperature and places 10min, at 60 ℃ of preheating 10min, and at 140 ℃ of heating 20min, film to solidify this bilayer simultaneously, obtain test plate (panel).
Test plate (panel) to above gained carries out following performance test.
The film coated surface slickness: the slickness of film coated surface is measured with Wave Scan (trade(brand)name, BYK GardnerCo.).Wave Scan energy measurement long wave value (LW) and shortwave value (SW).
The long wave value is that wavelength region is the scintillation index of the surfaceness of 1.2～12mm, can estimate the macrorelief of film coated surface orange peel and so on.The shortwave value is that wavelength region is the scintillation index of the surfaceness of 0.3～1.2mm, can estimate the little fluctuating of film coated surface microtexture.
About these 2 Wave Scan values, less observed value shows the slickness that film coated surface is higher.
Gloss: gloss is estimated as follows by visual inspection
Zero: good
△: good inadequately
*: poor
Acid resistance: on the coatingsurface of each test plate (panel), drip and go up 0.5ml 40% aqueous sulfuric acid, use Gradient Oven (trade(brand)name, BYK Gardner Co.) then at 80 ℃ of heating 30min.Water cleans this surface then, and estimates the state of coating surface by following criterion:
Zero: do not observe appearance of film and change or corrode, good
Zero △: do not observe appearance of film and change but slightly corroded
△: observe appearance of film and change and corrode on a small quantity
*: observe film serious appearance change and corrosion
The preparation of test plate (panel) 2 (jaundice that anti-paint baking over causes)
After forming electrocoating film, follow the preparation process of test plate (panel) 1.On electrocoating film, the water base intermediate coat of aerial spraying (WP 305T#62 First Base, trade(brand)name, Kansai Paint Co., the automobile water base intermediate coat of vibrin-melmac, join function based on the CIE look, the L value of its whiteness is 85) to thickness be 35 μ m, stay under the room temperature and treat 5min, at 80 ℃ of preheating 10min, at 150 ℃ of 30min that are heating and curing, film with in the middle of forming.
On filming in the centre, coating water-based primer (WBC 713T#062 Second Base, trade(brand)name, Kansai Paint Co., automobile is with acrylic resin-melmac mica priming paint) to thickness be 15 μ m, stay under the room temperature and treat 5min, and at 80 ℃ of preheating 10min.On this uncured mica bottom coating among above embodiment of separate application and the comparative example 1# of gained～transparent decorations of 24# water-based single-component coat with lacquer to thickness respectively be 40 μ m, stay under the room temperature and treat 10min, at 80 ℃ of preheating 10min, and solidify this bilayer 30min that films simultaneously by being heated to 140 ℃, so that test plate (panel) to be provided.
Downcut a part so that on-gauge plate to be provided from each test plate (panel).The rest part of test plate (panel) at 160 ℃ of reheat 50min.
After 160 ℃ of 50min heating, join function according to the CIE look, measure the Δ b value of test plate (panel) and on-gauge plate, the anti-jaundice that causes because of paint baking over this assess sample.The less more anti-paint baking over of Δ b value representation causes jaundice.The measurement of Δ b value is carried out with Color Guide 45/0 (trade(brand)name, BYKGardner Co.).
The preparation of test plate (panel) 3 (no sand resurfacing agglomerability)
Same steps as by the above test plate (panel) 1 of preparation prepares test plate (panel), but the final heating condition that priming paint and this bilayer of Clear coating are filmed is changed at 160 ℃ of paint baking over 30min.At the coatingsurface of these paint baking over test plate (panel)s, be coated on identical priming paint used in the preparation of test plate (panel) 1 and water-based single-component Clear coating again.The heating condition that prime coat and this bilayer of Clear coating are filmed changes at 130 ℃ of heating 30min.Repeat to prepare decorations lacquer coating, preheating and the thermal cure step of test plate (panel) 1 in addition, obtain being used to estimate the test plate (panel) of no sand resurfacing agglomerability.
At each face of the test plate (panel) of estimating no sand resurfacing agglomerability, draw to reaching base deeply with the cutting knife intersection, mark 100 2mm * 2mm square.Sticking glass paper tape on these 100 squares is peelled off rapidly then.Non--sandblast is coated with agglomerability again and upward keeps int square to count evaluation by filming.Evaluation criteria is as follows:
Zero: keeping the square number is 100
Zero △: keep the square number and be not less than 90 but less than 100
△: keep the square number and be not less than 50 but less than 90
*: keep the square number less than 50.
Table 2 and 3 has provided simultaneously to coating surface slickness, gloss, acid resistance, the anti-jaundice that causes because of paint baking over and the above-mentioned evaluation result of not having sand resurfacing agglomerability.
Figure A20081008349300331
Figure A20081008349300341
Figure A20081008349300361

Claims (14)

1. water-based single-component paint is characterized in that it is the decorations coating compositions that comprises following component
(1) acrylic resin (A) by the following component gained of copolymerization
(a) (methyl) acrylate of at least a hydroxyl by following formula (I) expression of 20～60 quality %:
Figure A20081008349300021
Wherein,
R 1Represent hydrogen or methyl and
R 2Represent C at least 4Uncle's hydroxyalkyl, C at least 4The organic substituent of primary hydroxyl polyoxyalkylene or following formula (II) expression
Figure A20081008349300022
Wherein, R 3Represent hydrogen or methyl, 1 is 2～5 integer, and k is 1～7 integer;
(b) at least a vinyl monomer that contains carboxyl, sulfonic group or phosphate of 0.7～15 quality %; With
(c) but at least a other copolyethylene monomer of 25～79.3 quality %;
Described tree refers to that the hydroxyl value of (A) is that 110～200mgKOH/g and acid number are 5～50mgKOH/g;
With
(2) at least a blocked polyisocyanates compound (B)
Also be, the solubility parameters (SP1) of acrylic resin (A) is 9.30～11.20, the solubility parameters (SP2) of blocked polyisocyanates compound (B) is 9.00～11.50, and the difference Δ SP (Δ SP=(SP1)-(SP2)) of the solubility parameters (SP2) of the solubility parameters (SP1) of acrylic resin (A) and blocked polyisocyanates compound (B) is in-0.8～1.50 scopes.
Blocked polyisocyanates compound (B) comprise the end capped polyisocyanate compound of azole compounds and
This decorations coating compositions also includes machine tin compound and/or bismuth compound as catalyzer.
2. according to the water-based single-component paint of claim 1, wherein the hydroxyl value of acrylic resin (A) is that 120～180mgKOH/g and acid number are 10～40mgKOH/g.
3. according to the water-based single-component paint of claim 1, wherein the solubility parameters (SP1) of acrylic resin (A) is 9.50～11.00.
4. according to the water-based single-component paint of claim 1, wherein the solubility parameters (SP2) of blocked polyisocyanates compound (B) is 9.20～10.50.
5. according to the water-based single-component paint of claim 1, wherein the difference Δ SP (Δ SP=(SP1)-(SP2)) of the solubility parameters (SP2) of the solubility parameters (SP1) of acrylic resin (A) and blocked polyisocyanates compound (B) is in 0.5～1.20 scope.
6. according to the water-based single-component paint of claim 1, wherein blocked polyisocyanates compound (B) comprises the end capped polyisocyanate compound of 3.
7. according to the water-based single-component paint of claim 1, wherein the equivalence ratio (NCO/OH) of isocyanate group in the blocked polyisocyanates based compound (B) and the hydroxyl in the acrylic resin (A) is 0.5～1.0.
8. according to the water-based single-component paint of claim 1, wherein for the combined solid content of per 100 mass parts acrylic resins (A) and blocked polyisocyanates compound (B), it contains 0.01～10 mass parts organo-tin compound and/or bismuth compound.
9. according to the water-based single-component paint of claim 1, it also contains hindered amine as light stabilizer.
10. according to the water-based single-component paint of claim 1, the average particulate diameter that wherein is present in the discrete particles in the decorations coating compositions is 100～500nm.
11. according to the water-based single-component paint of claim 1, the mass concentration of its solids content be 40～60% and VOC content be 0～300g/l.
12. the multilayer film forming method is included in and wants on the coated object successively to be coated with one deck priming paint and layer of transparent decorations lacquer at least at least, it is characterized in that being coated with that any one described water-based single-component paint coats with lacquer as the transparent decorations of cover in the claim 1～11.
13. multilayer film forming method, be included in and want on the coated object coated heat solidity water base paint compositions as priming paint, any one described water-based single-component paint coats with lacquer as transparent decorations in uncured coatingsurface coating claim 1～11, then while cured base coating and Clear coating.
14. method articles coated according to claim 12 or 13.
CNA2008100834934A 2007-03-08 2008-03-07 Water-based single-component paint and multilayer film forming method Pending CN101260272A (en)

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